CA1230448A - Polyisocyanurate foams prepared from partially etherified methylolamines - Google Patents
Polyisocyanurate foams prepared from partially etherified methylolaminesInfo
- Publication number
- CA1230448A CA1230448A CA000453793A CA453793A CA1230448A CA 1230448 A CA1230448 A CA 1230448A CA 000453793 A CA000453793 A CA 000453793A CA 453793 A CA453793 A CA 453793A CA 1230448 A CA1230448 A CA 1230448A
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- Prior art keywords
- acid
- cxh2x
- foam
- prepared
- partially etherified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
POLYISOCYANURATE FOAMS PREPARED FROM
PARTIALLY ETHERIFIED METHYLOLAMINES
Abstract of the Disclosure Polyisocyanurate foams are prepared from reacting partially etherified methylolmelamines either alone or in mixture with polyoxyalkylene polyether polyols with polyiso-cyanates. Improved friability and flame retardancy are obtained.
PARTIALLY ETHERIFIED METHYLOLAMINES
Abstract of the Disclosure Polyisocyanurate foams are prepared from reacting partially etherified methylolmelamines either alone or in mixture with polyoxyalkylene polyether polyols with polyiso-cyanates. Improved friability and flame retardancy are obtained.
Description
~3~ 1401 POLYISOCYANURATE FOAMS PREPARED FROM
PARTIALLY ETHERIFIED METHYLOLAMINES
Background of the Invention 1. Field of the Invention ~ The present invention relates to polyisocyanurate foams prepared from partially etherified methylolamines with polyisocyanates in the presence of trimerization cataly3ts.
PARTIALLY ETHERIFIED METHYLOLAMINES
Background of the Invention 1. Field of the Invention ~ The present invention relates to polyisocyanurate foams prepared from partially etherified methylolamines with polyisocyanates in the presence of trimerization cataly3ts.
2. Description of the Prior Art -The prior art generally teache~ the preparation of isocyanurate-modified foam products.
U. S. Patent 4,139,501 teaches the preparation of polyurethane foam with enhanced flame retardancy by the reaction of a polyol and an organic polyisocyanate in mixture with a hydroxylmethylmelamine derivative and including therein a halogenated phosphorus ester.
U. S. Patent 4,197,373 teache~ the preparation of flame retardant polyurethane foams from a reaction mixture containing the reaction products of melamine and chloral and optionally alkylene oxide adducts thereof.
U. SO Patent 3,135,707 teaches the use of par-tially alkylated polymethylolmelamines for the preparation of polyurethane foams. There is no teaching in the prior art that improved flame retardant polyisocyanurate foams may be prepared employing partially etherified methylolmelamines either alone or in combination with ot~er polyol~.
U. S. Patent 4,139,501 teaches the preparation of polyurethane foam with enhanced flame retardancy by the reaction of a polyol and an organic polyisocyanate in mixture with a hydroxylmethylmelamine derivative and including therein a halogenated phosphorus ester.
U. S. Patent 4,197,373 teache~ the preparation of flame retardant polyurethane foams from a reaction mixture containing the reaction products of melamine and chloral and optionally alkylene oxide adducts thereof.
U. SO Patent 3,135,707 teaches the use of par-tially alkylated polymethylolmelamines for the preparation of polyurethane foams. There is no teaching in the prior art that improved flame retardant polyisocyanurate foams may be prepared employing partially etherified methylolmelamines either alone or in combination with ot~er polyol~.
3~ 8 Summary of the Invention The present invention proposes a new polylsocyanu-rate foam which is prepared reacting (a) a polyol, (b) an organic polyisocyanate, (c) blowing agent, in -the presence oE a -trimeriza-tion catalyst, wherein the polyol is selected from the group consisting of a partially etherified methyl-olmelamine and a mixture of a polyoxyalkylene polyether polyol and said methylolmelamine.
Description of the Preferred Embodiment The etherified methylolmelamine used as starting compound can be prepared by reacting an aqueous solution of lS formaldehyde with melamineemploying an alkaline catalyst.
After the reaction has proceeded at elevated temperatures, an etherifying hydroxyl containing compound is added, followed by an acid catalyst and the e-therification process is allowed to proceed. After the reaction is complete, the product is obtained by neutralization of the acid filtration of the salts, and vacuum stripping of the volatiles.
The etherified methylolmelamine employed in the invention is the condensation product of melamine and formalkehyde in the first stage of the reaction. In the second stage, etherification is accomplished by reacting an alcohol with the methylolmelamine to form a product having the following formula:
/ N~
2 n(RCH2)HnH-~ ~c-NH~(cH2R)2-n N ~ ~ N
NHn(~H2R)2-n ~' ~2~
wherein n is an integer from O to 2 R is selected from the group consisting of - -CxH2x+1 _ o CXH2XocxH2x ~ ~CxH2x-y+lYy - ~CzH2z 1 o - P-(OR')2 -- O-C H2 C-NH-CxH~x--OH~
HC - CH
Il 11 - O-CH -C CH and x 2x wherein y is an inteyer from 1 to 3 and R' is an alkyl containing 1 to 4 carbon atoms, x is an integer from 1 to 5, Y is bromine or chlorine, and z is an integer from 2 to 5 and with the proviso that at least two of the R groups are OH.
The preferred ratio of formaldehyde to melamine is 7:1 to 8:1 while the preferred ratio of alcohol to melamine is 13:1 to 15:1.
~Z~3~
Any alkaline catalyst may be employed. Examples include sodium hydroxide, potaqsium hydroxide, sodium methoxide etc. The acid catalyqts which may be employed are nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid. The hydroxyl group containing compounds which may be employed for the etherification are those which have the formula:
x 2x+1 HocxH2xocxH2xoH
CxH2x_y~ YyO
CZH2Z_10~1 HCxH2xNH R ~
Ho - c~H2x-NH-cxH2x-oH ~
H~ ~ IClH
HO-CH2- CH and \0/
HO Cx 2x wherein x, y, z, R' and Y are as defined above.
It iq further contemplated that compounds having the formula:
o ~_p-(OR')~
~23~8 may be employed wherein R' iq an alkyl radical containing from 1 to 4 carbon atom~.
The phosphorus compounds are generally employed in combination with the other compound~ liqted above in order to provide that at least two R groups are OH.
The partially etherified methylolmelamines are reacted with polyisocyanates in the presence of trimeri2a-tion catalysts and blowing agents to produce polyisocya-nurate foam~.
The organic polyisocyanate employed in the instant invention corre~ponds to the formula RltNco)z where R' i9 a polyvalent organic radical which is either aliphatic, aryl~
alkyl, alkylaryl, aromatic or mixtures thereof and z is an integer which corresponds to the valence of R' and is at lea~t 2~ Representative of the types of organic polyi50-cyanates contemplated herein include, for example, 1,2-diisocyanatoethane, 1,3-diisocyanatopropane, 1,2-dii~o-cyanatopropane, 1,4-diisocyanatobutane, 1,5-diisocyanato-pentane, 1,6-diisocyanatohexane, bis~3-isocyanatopropyl)-ether, bi.Y(3-isocyanatopropyl)qulfide, 1,7-diisocyanato-heptane, 1,5-diisocyanato-2,2-dimethylpentane, 1,6-diiso-cyanate-3-methoxyhexane, 1,8-diisocyantooctane, 1,5 diiso-cyanato-2,2,4-trimethylpentane, l,9-diisocyanatononane, l,10-dii~ocyanatopropyl ether of 1,4-butylene glycol, 1,11 diisocyanatoundecane, 1,12-diisocyanatododecane, bis~iso-~3~
cyanatohexyl) sulfide, 1,4-diisocyanatobenzene, 1,3-diiso-cyanato-o-xylene, 1,3-diisocyanato-p-xylene, 1,3-diiso-cyanate-m-xylene, 2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-l-nitrobenzene, 2,5-diisocyanato-1-nitro-benzene, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetra-methylene diisocyanate, 1,4~cyclohexane diisocyanate, hexa-hydrotoluene diisocyanate, 1,5-naphthylene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dime~hyl-4,4'-diphenylmethane diiso-cyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, the triisocyanates such as 4,4l,4"-triphenylmethane triiso-cyanate, polymethylene polyphenylene polyisocyanate and 2,4,6-toluene triisocyanate' and the tetraisocyanates such as 4,4'-dimethyl-2,2'-5,5'-diphenylmethane tetraisocya-nate. Especially u~eful due to their availability and properties are toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, poly-methylene polyphenylene polyisocyanate and mixture~ thereof.
~ he polyisocyanurate foams of the instant inven-tion may be prepared by employing well-known compounds aa trimerization catalysts. Examples of these catalysts are ~23~
(a) organic strong bases, (b) tertiary amine co-catalyst combinations, (c) Friedel Craft catalsyts, (d) ba~ic salts of carboxylic acids, (e) alkali metal oxides, alkali metal alcoholates, alkali metal phenolates, alkali metal hy-droxides and alkal metal carbonates, (f) onium compounds from nitrogen, phosphorus, arsenic, antimony, ~ulfur and selenium, and (g) mono-substituted monocarbamic es~ers.
Th~e include 1,3,5-triq(N,N-dialkylaminoalkyl)-s-hexahydro-triazines, the alkylene oxide and water additives of 1,3,5-tris(N,N dialkylaminoalkyl)-s-hexahydrotriazines; 2,4,6-tris(dimethylaminomethyl)phenol; ortho, para- or a mixture of o- and p-dimethylaminomethyl phenol and triethylene-diamine or the alkylene oxide and water adduct~ thereof, metal carboxylates such as potas~ium octanoate, sodium and potassium salt~ of hydroxamic acid, and organic boron-containing compounds. Monofunctional alkanol3 containing from 1 to 24 carbon atom~, epoxides containing 2 to 18 carbon atom~ and alkyl carbonates may be u~ed in conjunction with tertiary amine to accelerate the rate of the polymeri-zation reaction. The concentration of trimerizationcatalysts that may be employed in the present invention is from 0.001 part to 20 parts of cataly~t per 100 parts of organic polyi~ocyanate. The temperature range~ which may be employed for the polymerization reaction may range from 25C
to 230C, preferably from 15C to 120C.
~;~3~
In accordance with the present invention, rigid, flexible, and microcellular foams may be prepared by the catalytic reaction of organic polyisocyanates with polyol~
containing therein the etherified methylolmelamine in the presence of blowing agents, trimerization catalysts, qurfac~
tant~ and other additives which may be deemed neces~ary.
Non-cellular products may also be prepared in the absence of blowing agentsO
Typical optional polyols which may be employed in the preparation of the foams of the instant invention include polyhydroxyl-containing polyesters, polyoxyalkylene polyether polyol~, polyhydroxy-terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds, and alkylene oxide adducts of polyhydric sulfur-containing esters, polyacetals, aliphatic polyol~ or diols, ammonia, and amine~ including aromatic, aliphatic and heterocyclic amines as well a~ mixtures thereof. Alkylene oxide adducts of compounds which contain two or more different groups within the above-defined clas~es may also be used such a~
amino alcohol~ which contain an amino group and a hydroxyl yroup. Also, alkylene oxide adduct~ of compound~ which contain one -SH group and one -OH group a~ well as those which contain an amino group and a -SH group may be used.
Generally, the equivalent weight of the polyols will vary from lOO to lO,OOO, preferably from lOOO to 3000~
~3~
Any suitable hydroxy-terminated polyester may be used such as are obtained, for example, from the reaction of polycarboxylic acids and polyhydric alcohols. Any suitable polycarboxylic acid may be used such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, a-hydromuconic acid, ~-butyl-~ethyl-glutaric acid, ~,~-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid, and 1,4-cyclohexanedicarboxylic acid. Any suitable polyhydric alcohol may be used such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, l,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol, l,l,l-trimethylolpropane, 1,1,1-trimethylolethane, l,2,6-hexanetriol, ~-methyl glucoside, pentaerythritol,and sorbitol. Also included within the term "polyhydric alcohol" are compounds derived from phenol such a~ 2,2-bi~(4-hydroxyphenyl)propane, commonly known as Bisphenol A.
Any suitable polyoxyalkylene polyether polyol may be used such as the polymerization product of an alkylene oxide with a polyhydric alcohol~ Any suitable polyhydric alcohol may be used such as those disclosed above for use in the preparation of the hydroxy-terminated polyesters. Any ~3~
suitable alkylene oxide may be used such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of these oxides. The polyalkylene polyethQr polyols may be prepared from other starting materials such as tetrahydro-furan and alkylene oxide-tetrahydrofuran mixtures, epihalo-hydrins ~uch as epichlorohydrin, as well as aralkylene oxides such as styrene oxide. The polyalkylene polyether polyols may have eîther primary or secondary hydroxyl groups. Included among the polyether polyol~ are polyoxy-ethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combination~ of polyoxypropylene and polyoxy-ethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols, poly-1,4-tetramethylene and polyoxyethylene glycols,and copolymer glycols prepared from blends as well as sequential addition of two or more alkylene oxides. The polyalkylene polyether polyols may be prepared by any known process such as, for example, the proces di~closed by Wurtz in 1859 and Encyclopedia of_Chemical Technolog~, Vol. 7, pp.
257-262, published by Interscience Publishers, Inc. (1951) or in U.S. Patent No. 1,922,459. Polyethers which are preferred include the alkylene oxide addition products of ~rimethylolpropane, glycerine, pentaerythritol, sucrose, sorbitol, propylene glycol, and 2,2-bis(4-hydroxyphenyl)-propane and blends thereof having equivalent weights of from lOO to 5000.
~L2;3~
Suitable polyhydric polythioethers which may be condensed with alkylene oxides include the condensation product of thiodiglycol or the reaction product of a dicarboxylic acid such as is disclo~ed above for the preparation of the hydroxyl-containing polyester~ with any other suitable thioether glycol.
The hydroxyl-containing polyester may also be a polyester amide such as i9 obtained by including some amine or amino alcohol in the reactants for the preparation of the polye~ters. Thus, polyester amicles may be obtained by condensing an amino alcohol ~uch as ethanolamine with the polycarboxylic acids set forth above or they may be made using the same components that make up the hydroxyl-contain-ing polyester with only a portion of the components being a diamine such a3 ethylene diamine.
Polyhydroxyl-containing phosphorus compounds which may be used include those compounds disclosed in U.S. Patent No. 3,639,542. Preferred polyhydroxyl-containing phosphorus compound~ are prepared from alkylene oxides and acids of phosphorus having a P2O5 equivalency of from about 72 percent to about 95 percent.
Suitable polyacetals which may be condensed wi~h alkylene oxides include the reaction product of formaldehyde or other suitable aldehyde with a dihydric alcohol or an alkylene oxide ~uch as those disclosed above.
Suitable aliphatic thiols ~hich may be condensed with alkylene oxides include alkanethiols containing at least two -SH groups sucha 9 1,2-ethanedithiol, 1,2-propane-dithiol, 1,2-propanedithiol, and 1,6-hexanedithiol, alkene thiols ~uch as 2-butene~1,4-dithiol, and alkyne thiols such as 3-hexyne-1,6-dithiol.
Suitable amines which may be condensed with alkylene oxides include aromatic amines such as aniline, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, methylene dianiline, the condensation products of aniline and formaldehyde, and diaminotoluene, aliphatic amine~ such as methylamine, triisopropanolamine, ethylene diamine, 1,3-diaminopropane, l,3-diaminobutane,and 1,4-diaminobutane.
Water, low boiling hydrocarbons such as pentane, hexane, heptane, pentene, and heptene, azo compounds such aq azohexahydrobenzodinitrile, halogenated hydrocarbons 3uch as dichlorodifluoromethane, trichlorofluoromethane, dichlorodi-fluoroethane, vinylidene chloride, and methylene chloride may be used as blowing agentsO
Chain-extendin~ agents which may be employed in the preparation of the polyurethane foams include those compounds having at least two functional groups bearing active hydrogan atoms such as water, hydrazine, primary and secondary diamines, amino alcohols, amino acids, hydroxy acids, glycols, or mixtures thereof. A preferred group of chain-extending agents includes water, ethylene glycol, 1,4-butanediol, and primary and secondary diamines which react more readily with the polyisocyanates than does water.
These include phenylenedlamine~ ethylenediamine, diethylene-triamine, N-(2-hydroxypropyl)-ethylenediamine, N,N'-di(2-hydroxypropyl)ethylenediamine, piperazine, and 2-methyl-piperazine.
A surface-active agent is generally necessary for production of high grade polyurethane foam according to the present invention, since in the absence of same, the foams collapse or contain very large uneven cells. Numerous surface-active agents have been found satisfactory.
Nonionic surface-active agents are preferred. Of these, the nonionic surface-active agents such as the well-known silicones have been found particularly desirable. Other surface-active agents which are operative, although not preferred, include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonic esters, and alkyl arylsulfonic acids.
In the following examples, all parts are by weight unless otherwise designated and the following abbreviations are employed.
~LZ3~
Etherlfying agent A - butanol B - methanol C - dibromopropanol D - trichloroethanol E - 2-ethoxyethanol F - furfuryl alcohol G - allyl alcohol H - 2-chloroethanol I - diethylene glycol J - diethanolamine K - diethylphosphite L - N-methylethanolamine Polyol A - a propylene oxide adduct of pentaerythritol having a hydroxyl number of 400.
Freon llA - monochlorotrifluoromethane sold by E. I.
duPont de Wemours & Co.
L-5303 - a silicone ~urfactant TDH - 1,3,5-tri~(N,N-dimethylaminopropyl)-S-hexahydrotriazine T-9 - stannouY 2-ethylhexanoate * Trademark ~3~
Examples 1-12 Into a suitable reaction veqsel equipped with a stirrer, reflux conden~er, and thermometer wa~ added formaldehyde, melamine, neutralized formalin ~olution and one-half of the etharifyi~g agent or mixtures thereof in the amounts indicated in the Table below. The amount of ~odium hydroxide varied from 0.75 pbw to 2.0 pbw. The mixture was heated to about 55C for two hour~. After cooling, the remaining amount of etherifying agent was added and the mixture was heated to 35C. The alkaline catalyst was neutralized with nitric acid, the reaction solution was then vacuum stripped at 50~C to remove all volatiles. The residue was then washed with methylene chloride, filtered, and the product obtained by vacuum stripping the volatiles at 50C.
-~5-~L~3~
~o ~ ~ ~n ~ ~ I~ ~ ~ ~ ~ co O ~ ~ r~ ~ ~ ~ ~ ~ ~ I` I
Q
C
a O O N ~ ~J o O ~ D O In ~0 0 ~ Q
a~ ~1 ~ ~ o ~ co co 1~ ~ o co o ~ ~ I 1~ O
~i ~ ~ ~ ~ ~ ~ ) O ~ 1-1 ~ O ~ ) N
~: m :Q V m ~ ~ ELI ~ 3 ~ H a:l 1~ ~ Pa .
~1 ~
o ~ ~ ~ ~ o W ~
~) d ' ~ c~ ~ O
~1 Examples 13-24 The designated resin, with or without added Polyol A (300 pbw), 9.0 pbw Freon llA, 4 parts ~-5303, 2.1 parts TDH catalyst and 0.1 parts of T-9 catalyst were mixed for 30 3econds. Crude MDI wa~ added, the mixture wa~
stirred for 10 seconds and the entire mixture poured into a one-gallon container and the foam was allowed to rise. The re3ulting foams were cured at room temperature for 25 hours. The re3ins employed and the resulting physical properties o~ the foams are shown in Table II below.
Improvements in smoke den3ity, friability and weight retained in the Butler chimney test are shown when the resin~ of the invention are employed.
G C ) In In c~
8 ~ ~, ~ ~ ~, ~ ~ ~
'r ~ ~ O~ r ~
~ U~ O ~0 n ~ ~ 8 a~o ~ _~
~1 o ' o ~1~. l` ~ 1` ' 8~ ~ ~ ~ ~ o ~ a~ u~
o In ~ ~ In n~ ~ ~ ~
'~ D (n $ t`
o ~ ~ ~ ~ ~1 ,, (n 0 U~ E
~q S O
,~, R ~ U
Description of the Preferred Embodiment The etherified methylolmelamine used as starting compound can be prepared by reacting an aqueous solution of lS formaldehyde with melamineemploying an alkaline catalyst.
After the reaction has proceeded at elevated temperatures, an etherifying hydroxyl containing compound is added, followed by an acid catalyst and the e-therification process is allowed to proceed. After the reaction is complete, the product is obtained by neutralization of the acid filtration of the salts, and vacuum stripping of the volatiles.
The etherified methylolmelamine employed in the invention is the condensation product of melamine and formalkehyde in the first stage of the reaction. In the second stage, etherification is accomplished by reacting an alcohol with the methylolmelamine to form a product having the following formula:
/ N~
2 n(RCH2)HnH-~ ~c-NH~(cH2R)2-n N ~ ~ N
NHn(~H2R)2-n ~' ~2~
wherein n is an integer from O to 2 R is selected from the group consisting of - -CxH2x+1 _ o CXH2XocxH2x ~ ~CxH2x-y+lYy - ~CzH2z 1 o - P-(OR')2 -- O-C H2 C-NH-CxH~x--OH~
HC - CH
Il 11 - O-CH -C CH and x 2x wherein y is an inteyer from 1 to 3 and R' is an alkyl containing 1 to 4 carbon atoms, x is an integer from 1 to 5, Y is bromine or chlorine, and z is an integer from 2 to 5 and with the proviso that at least two of the R groups are OH.
The preferred ratio of formaldehyde to melamine is 7:1 to 8:1 while the preferred ratio of alcohol to melamine is 13:1 to 15:1.
~Z~3~
Any alkaline catalyst may be employed. Examples include sodium hydroxide, potaqsium hydroxide, sodium methoxide etc. The acid catalyqts which may be employed are nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid. The hydroxyl group containing compounds which may be employed for the etherification are those which have the formula:
x 2x+1 HocxH2xocxH2xoH
CxH2x_y~ YyO
CZH2Z_10~1 HCxH2xNH R ~
Ho - c~H2x-NH-cxH2x-oH ~
H~ ~ IClH
HO-CH2- CH and \0/
HO Cx 2x wherein x, y, z, R' and Y are as defined above.
It iq further contemplated that compounds having the formula:
o ~_p-(OR')~
~23~8 may be employed wherein R' iq an alkyl radical containing from 1 to 4 carbon atom~.
The phosphorus compounds are generally employed in combination with the other compound~ liqted above in order to provide that at least two R groups are OH.
The partially etherified methylolmelamines are reacted with polyisocyanates in the presence of trimeri2a-tion catalysts and blowing agents to produce polyisocya-nurate foam~.
The organic polyisocyanate employed in the instant invention corre~ponds to the formula RltNco)z where R' i9 a polyvalent organic radical which is either aliphatic, aryl~
alkyl, alkylaryl, aromatic or mixtures thereof and z is an integer which corresponds to the valence of R' and is at lea~t 2~ Representative of the types of organic polyi50-cyanates contemplated herein include, for example, 1,2-diisocyanatoethane, 1,3-diisocyanatopropane, 1,2-dii~o-cyanatopropane, 1,4-diisocyanatobutane, 1,5-diisocyanato-pentane, 1,6-diisocyanatohexane, bis~3-isocyanatopropyl)-ether, bi.Y(3-isocyanatopropyl)qulfide, 1,7-diisocyanato-heptane, 1,5-diisocyanato-2,2-dimethylpentane, 1,6-diiso-cyanate-3-methoxyhexane, 1,8-diisocyantooctane, 1,5 diiso-cyanato-2,2,4-trimethylpentane, l,9-diisocyanatononane, l,10-dii~ocyanatopropyl ether of 1,4-butylene glycol, 1,11 diisocyanatoundecane, 1,12-diisocyanatododecane, bis~iso-~3~
cyanatohexyl) sulfide, 1,4-diisocyanatobenzene, 1,3-diiso-cyanato-o-xylene, 1,3-diisocyanato-p-xylene, 1,3-diiso-cyanate-m-xylene, 2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-l-nitrobenzene, 2,5-diisocyanato-1-nitro-benzene, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetra-methylene diisocyanate, 1,4~cyclohexane diisocyanate, hexa-hydrotoluene diisocyanate, 1,5-naphthylene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dime~hyl-4,4'-diphenylmethane diiso-cyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, the triisocyanates such as 4,4l,4"-triphenylmethane triiso-cyanate, polymethylene polyphenylene polyisocyanate and 2,4,6-toluene triisocyanate' and the tetraisocyanates such as 4,4'-dimethyl-2,2'-5,5'-diphenylmethane tetraisocya-nate. Especially u~eful due to their availability and properties are toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, poly-methylene polyphenylene polyisocyanate and mixture~ thereof.
~ he polyisocyanurate foams of the instant inven-tion may be prepared by employing well-known compounds aa trimerization catalysts. Examples of these catalysts are ~23~
(a) organic strong bases, (b) tertiary amine co-catalyst combinations, (c) Friedel Craft catalsyts, (d) ba~ic salts of carboxylic acids, (e) alkali metal oxides, alkali metal alcoholates, alkali metal phenolates, alkali metal hy-droxides and alkal metal carbonates, (f) onium compounds from nitrogen, phosphorus, arsenic, antimony, ~ulfur and selenium, and (g) mono-substituted monocarbamic es~ers.
Th~e include 1,3,5-triq(N,N-dialkylaminoalkyl)-s-hexahydro-triazines, the alkylene oxide and water additives of 1,3,5-tris(N,N dialkylaminoalkyl)-s-hexahydrotriazines; 2,4,6-tris(dimethylaminomethyl)phenol; ortho, para- or a mixture of o- and p-dimethylaminomethyl phenol and triethylene-diamine or the alkylene oxide and water adduct~ thereof, metal carboxylates such as potas~ium octanoate, sodium and potassium salt~ of hydroxamic acid, and organic boron-containing compounds. Monofunctional alkanol3 containing from 1 to 24 carbon atom~, epoxides containing 2 to 18 carbon atom~ and alkyl carbonates may be u~ed in conjunction with tertiary amine to accelerate the rate of the polymeri-zation reaction. The concentration of trimerizationcatalysts that may be employed in the present invention is from 0.001 part to 20 parts of cataly~t per 100 parts of organic polyi~ocyanate. The temperature range~ which may be employed for the polymerization reaction may range from 25C
to 230C, preferably from 15C to 120C.
~;~3~
In accordance with the present invention, rigid, flexible, and microcellular foams may be prepared by the catalytic reaction of organic polyisocyanates with polyol~
containing therein the etherified methylolmelamine in the presence of blowing agents, trimerization catalysts, qurfac~
tant~ and other additives which may be deemed neces~ary.
Non-cellular products may also be prepared in the absence of blowing agentsO
Typical optional polyols which may be employed in the preparation of the foams of the instant invention include polyhydroxyl-containing polyesters, polyoxyalkylene polyether polyol~, polyhydroxy-terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds, and alkylene oxide adducts of polyhydric sulfur-containing esters, polyacetals, aliphatic polyol~ or diols, ammonia, and amine~ including aromatic, aliphatic and heterocyclic amines as well a~ mixtures thereof. Alkylene oxide adducts of compounds which contain two or more different groups within the above-defined clas~es may also be used such a~
amino alcohol~ which contain an amino group and a hydroxyl yroup. Also, alkylene oxide adduct~ of compound~ which contain one -SH group and one -OH group a~ well as those which contain an amino group and a -SH group may be used.
Generally, the equivalent weight of the polyols will vary from lOO to lO,OOO, preferably from lOOO to 3000~
~3~
Any suitable hydroxy-terminated polyester may be used such as are obtained, for example, from the reaction of polycarboxylic acids and polyhydric alcohols. Any suitable polycarboxylic acid may be used such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, a-hydromuconic acid, ~-butyl-~ethyl-glutaric acid, ~,~-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid, and 1,4-cyclohexanedicarboxylic acid. Any suitable polyhydric alcohol may be used such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, l,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol, l,l,l-trimethylolpropane, 1,1,1-trimethylolethane, l,2,6-hexanetriol, ~-methyl glucoside, pentaerythritol,and sorbitol. Also included within the term "polyhydric alcohol" are compounds derived from phenol such a~ 2,2-bi~(4-hydroxyphenyl)propane, commonly known as Bisphenol A.
Any suitable polyoxyalkylene polyether polyol may be used such as the polymerization product of an alkylene oxide with a polyhydric alcohol~ Any suitable polyhydric alcohol may be used such as those disclosed above for use in the preparation of the hydroxy-terminated polyesters. Any ~3~
suitable alkylene oxide may be used such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of these oxides. The polyalkylene polyethQr polyols may be prepared from other starting materials such as tetrahydro-furan and alkylene oxide-tetrahydrofuran mixtures, epihalo-hydrins ~uch as epichlorohydrin, as well as aralkylene oxides such as styrene oxide. The polyalkylene polyether polyols may have eîther primary or secondary hydroxyl groups. Included among the polyether polyol~ are polyoxy-ethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combination~ of polyoxypropylene and polyoxy-ethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols, poly-1,4-tetramethylene and polyoxyethylene glycols,and copolymer glycols prepared from blends as well as sequential addition of two or more alkylene oxides. The polyalkylene polyether polyols may be prepared by any known process such as, for example, the proces di~closed by Wurtz in 1859 and Encyclopedia of_Chemical Technolog~, Vol. 7, pp.
257-262, published by Interscience Publishers, Inc. (1951) or in U.S. Patent No. 1,922,459. Polyethers which are preferred include the alkylene oxide addition products of ~rimethylolpropane, glycerine, pentaerythritol, sucrose, sorbitol, propylene glycol, and 2,2-bis(4-hydroxyphenyl)-propane and blends thereof having equivalent weights of from lOO to 5000.
~L2;3~
Suitable polyhydric polythioethers which may be condensed with alkylene oxides include the condensation product of thiodiglycol or the reaction product of a dicarboxylic acid such as is disclo~ed above for the preparation of the hydroxyl-containing polyester~ with any other suitable thioether glycol.
The hydroxyl-containing polyester may also be a polyester amide such as i9 obtained by including some amine or amino alcohol in the reactants for the preparation of the polye~ters. Thus, polyester amicles may be obtained by condensing an amino alcohol ~uch as ethanolamine with the polycarboxylic acids set forth above or they may be made using the same components that make up the hydroxyl-contain-ing polyester with only a portion of the components being a diamine such a3 ethylene diamine.
Polyhydroxyl-containing phosphorus compounds which may be used include those compounds disclosed in U.S. Patent No. 3,639,542. Preferred polyhydroxyl-containing phosphorus compound~ are prepared from alkylene oxides and acids of phosphorus having a P2O5 equivalency of from about 72 percent to about 95 percent.
Suitable polyacetals which may be condensed wi~h alkylene oxides include the reaction product of formaldehyde or other suitable aldehyde with a dihydric alcohol or an alkylene oxide ~uch as those disclosed above.
Suitable aliphatic thiols ~hich may be condensed with alkylene oxides include alkanethiols containing at least two -SH groups sucha 9 1,2-ethanedithiol, 1,2-propane-dithiol, 1,2-propanedithiol, and 1,6-hexanedithiol, alkene thiols ~uch as 2-butene~1,4-dithiol, and alkyne thiols such as 3-hexyne-1,6-dithiol.
Suitable amines which may be condensed with alkylene oxides include aromatic amines such as aniline, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, methylene dianiline, the condensation products of aniline and formaldehyde, and diaminotoluene, aliphatic amine~ such as methylamine, triisopropanolamine, ethylene diamine, 1,3-diaminopropane, l,3-diaminobutane,and 1,4-diaminobutane.
Water, low boiling hydrocarbons such as pentane, hexane, heptane, pentene, and heptene, azo compounds such aq azohexahydrobenzodinitrile, halogenated hydrocarbons 3uch as dichlorodifluoromethane, trichlorofluoromethane, dichlorodi-fluoroethane, vinylidene chloride, and methylene chloride may be used as blowing agentsO
Chain-extendin~ agents which may be employed in the preparation of the polyurethane foams include those compounds having at least two functional groups bearing active hydrogan atoms such as water, hydrazine, primary and secondary diamines, amino alcohols, amino acids, hydroxy acids, glycols, or mixtures thereof. A preferred group of chain-extending agents includes water, ethylene glycol, 1,4-butanediol, and primary and secondary diamines which react more readily with the polyisocyanates than does water.
These include phenylenedlamine~ ethylenediamine, diethylene-triamine, N-(2-hydroxypropyl)-ethylenediamine, N,N'-di(2-hydroxypropyl)ethylenediamine, piperazine, and 2-methyl-piperazine.
A surface-active agent is generally necessary for production of high grade polyurethane foam according to the present invention, since in the absence of same, the foams collapse or contain very large uneven cells. Numerous surface-active agents have been found satisfactory.
Nonionic surface-active agents are preferred. Of these, the nonionic surface-active agents such as the well-known silicones have been found particularly desirable. Other surface-active agents which are operative, although not preferred, include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonic esters, and alkyl arylsulfonic acids.
In the following examples, all parts are by weight unless otherwise designated and the following abbreviations are employed.
~LZ3~
Etherlfying agent A - butanol B - methanol C - dibromopropanol D - trichloroethanol E - 2-ethoxyethanol F - furfuryl alcohol G - allyl alcohol H - 2-chloroethanol I - diethylene glycol J - diethanolamine K - diethylphosphite L - N-methylethanolamine Polyol A - a propylene oxide adduct of pentaerythritol having a hydroxyl number of 400.
Freon llA - monochlorotrifluoromethane sold by E. I.
duPont de Wemours & Co.
L-5303 - a silicone ~urfactant TDH - 1,3,5-tri~(N,N-dimethylaminopropyl)-S-hexahydrotriazine T-9 - stannouY 2-ethylhexanoate * Trademark ~3~
Examples 1-12 Into a suitable reaction veqsel equipped with a stirrer, reflux conden~er, and thermometer wa~ added formaldehyde, melamine, neutralized formalin ~olution and one-half of the etharifyi~g agent or mixtures thereof in the amounts indicated in the Table below. The amount of ~odium hydroxide varied from 0.75 pbw to 2.0 pbw. The mixture was heated to about 55C for two hour~. After cooling, the remaining amount of etherifying agent was added and the mixture was heated to 35C. The alkaline catalyst was neutralized with nitric acid, the reaction solution was then vacuum stripped at 50~C to remove all volatiles. The residue was then washed with methylene chloride, filtered, and the product obtained by vacuum stripping the volatiles at 50C.
-~5-~L~3~
~o ~ ~ ~n ~ ~ I~ ~ ~ ~ ~ co O ~ ~ r~ ~ ~ ~ ~ ~ ~ I` I
Q
C
a O O N ~ ~J o O ~ D O In ~0 0 ~ Q
a~ ~1 ~ ~ o ~ co co 1~ ~ o co o ~ ~ I 1~ O
~i ~ ~ ~ ~ ~ ~ ) O ~ 1-1 ~ O ~ ) N
~: m :Q V m ~ ~ ELI ~ 3 ~ H a:l 1~ ~ Pa .
~1 ~
o ~ ~ ~ ~ o W ~
~) d ' ~ c~ ~ O
~1 Examples 13-24 The designated resin, with or without added Polyol A (300 pbw), 9.0 pbw Freon llA, 4 parts ~-5303, 2.1 parts TDH catalyst and 0.1 parts of T-9 catalyst were mixed for 30 3econds. Crude MDI wa~ added, the mixture wa~
stirred for 10 seconds and the entire mixture poured into a one-gallon container and the foam was allowed to rise. The re3ulting foams were cured at room temperature for 25 hours. The re3ins employed and the resulting physical properties o~ the foams are shown in Table II below.
Improvements in smoke den3ity, friability and weight retained in the Butler chimney test are shown when the resin~ of the invention are employed.
G C ) In In c~
8 ~ ~, ~ ~ ~, ~ ~ ~
'r ~ ~ O~ r ~
~ U~ O ~0 n ~ ~ 8 a~o ~ _~
~1 o ' o ~1~. l` ~ 1` ' 8~ ~ ~ ~ ~ o ~ a~ u~
o In ~ ~ In n~ ~ ~ ~
'~ D (n $ t`
o ~ ~ ~ ~ ~1 ,, (n 0 U~ E
~q S O
,~, R ~ U
Claims (5)
1. A polyisocyanurate foam prepared by reacting (a) a polyol, (b) an organic polyisocyanate, (c) blowing agent, in the presence of a trimerization catalyst, wherein the polyol is selected from the group consisting of a partially etherified methylolmelamine and a mixture of a polyoxyalkylene polyether polyol and said methylolmelamine.
2. The foam of claim 1 wherein said methylolmel-amine has the formula wherein n is an integer from O to 2.
R is selected from the group consisting of - OH, - O-CxH2x+1, - O-CxH2xOCxH2xOH, - O-CxH2x-y+1Yy, - O-CzH2z-1, - - O-CxH2xNH-R', - O-CxH2x-NH-CxH2x-OH, and - O-CxH2x-O-R' wherein y is an integer from 1 to 3 and R' is an alkyl containing 1 to 4 carbon atoms. x is 1 to 5, Y is bromine or chlorine, z is an integer from 2 to 5 and provided that at least two R groups are OH.
R is selected from the group consisting of - OH, - O-CxH2x+1, - O-CxH2xOCxH2xOH, - O-CxH2x-y+1Yy, - O-CzH2z-1, - - O-CxH2xNH-R', - O-CxH2x-NH-CxH2x-OH, and - O-CxH2x-O-R' wherein y is an integer from 1 to 3 and R' is an alkyl containing 1 to 4 carbon atoms. x is 1 to 5, Y is bromine or chlorine, z is an integer from 2 to 5 and provided that at least two R groups are OH.
3. The foam of claim 1 wherein R is OH.
4. The foam of claim 1 wherein R is OCxH2xOH.
5. The foam of claim 1 wherein the NCO:OH index is from 150 to 400.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/531,867 US4455397A (en) | 1983-09-14 | 1983-09-14 | Polyisocyanurate foams prepared from partially etherified methylolamines |
| US531,867 | 1995-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1230448A true CA1230448A (en) | 1987-12-15 |
Family
ID=24119377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000453793A Expired CA1230448A (en) | 1983-09-14 | 1984-05-08 | Polyisocyanurate foams prepared from partially etherified methylolamines |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4455397A (en) |
| EP (1) | EP0146692A1 (en) |
| CA (1) | CA1230448A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4939182A (en) * | 1988-07-27 | 1990-07-03 | The Dow Chemical Company | Melamine-alkanolamine condensates and polyurethanes prepared therefrom |
| US9528269B2 (en) | 2014-06-09 | 2016-12-27 | Johns Manville | Roofing systems and roofing boards with non-halogenated fire retardant |
| US9815256B2 (en) | 2014-06-09 | 2017-11-14 | Johns Manville | Foam boards including non-halogenated fire retardants |
| US9523195B2 (en) | 2014-06-09 | 2016-12-20 | Johns Manville | Wall insulation boards with non-halogenated fire retardant and insulated wall systems |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3135707A (en) * | 1961-02-02 | 1964-06-02 | American Cyanamid Co | Polyurethane foam compositions modified with partially alkylated polymethylolmelamines |
| DE2348838A1 (en) * | 1973-09-28 | 1975-04-10 | Elastogran Gmbh | Fire-resistant polyurethanes for furnishing foam and insulation - contg. isocyanurate gps. and melamine as flame retardant |
| GB1546705A (en) * | 1975-06-23 | 1979-05-31 | Tenneco Chem | Production of polyurethane foam |
| US4197373A (en) * | 1978-12-22 | 1980-04-08 | Pennwalt Corporation | Melamine derivatives as flame retardants for polyurethanes |
-
1983
- 1983-09-14 US US06/531,867 patent/US4455397A/en not_active Expired - Lifetime
-
1984
- 1984-05-08 CA CA000453793A patent/CA1230448A/en not_active Expired
- 1984-09-05 EP EP84110543A patent/EP0146692A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US4455397A (en) | 1984-06-19 |
| EP0146692A1 (en) | 1985-07-03 |
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